Pretreating hydrocarbons to be isomerized



Jan.- 3, 1950 s. F. PERRY PRETREATING nYnnocAnoNs To BE Isomuzn Filed Dec.v 28, 1946 i( duuukm.

2 f IV NQ.. 2 I o@ G* if dankzofruhpv Stephen. *F-Perrg :inventor Ex Glitter-neg.;

Patented Jan. 3, 1950 PRETREATING HYDROCARBONS T BE ISOMERIZED Stephen F. Perry, Roselle, N. J., assignor t0 Standard Oil Development Company, a corporation of Delaware Application December 2s, 194s, serial No. 713,922

2 Claims. l This invention relates to the conversion of hydrocarbons, particularly the straight chain paramns, to produce the corresponding branched chain paraiilns by means of a catalytic isomerization reaction. More particularly, the invention 5 sulfur dioxide, aluminum chloride-hydrocarbon relates to the isomerization of normal hexane to complexes, nitrobenzene, furfural and the like has isohexanes by subjecting the normal hexane or been resorted to. United States Patent No. a hydrocarbon mixture containing normal hexane 2,260,279 of October 21, 1941, discloses the harm such as a light naphtha fraction boiling up to suiered in isomerizing normal parafllns where 160 F'. to the catalytic action of a Friedel-Crafts l0 appreciable quantities of aromatics are present in catalyst, either with or without the use of a suitthe feed stock. Drastically reduced yields of isoable carrier such as a porous alumina, and in the parailins were obtained where the feed stock conpresence of promotional amounts of a halogentained as little as 5% by volume of aromatics. containing promoter, for example a hydrogen It is therefore desirable to remove these mahalide such as hydrogen chloride or hydrogen broterials from'the feed stock preliminary to isomerimide, under isomerization reaction conditions. zation. This has previously been done by treat- The resultant product is found to be useful as a ment with fuming sulfuric acid, by hydrogenaconstituent of motor fuel for improving the tion and the like. It has now been found that octane number thereof. hydrogenation catalysts consisting of from 0.5 to

The isomerization of normal paraiiins to iso- 5%, preferably 2%, of palladium or platinum deparafilns in the presence of Friedel-Crafts type posited in alumina or other support of high surcatalysts, of which aluminum chloride is a typical face area are particularly eifective as hydrogenaexample, and in the presence of promotional tion catalysts in removing aromatic compounds at amounts of halogen-containing promoters, of relatively mild conditions. It is particularly dewhich hydrogen chloride is a typical example, is sirable that the hydrogenation be carried out in old. Numerous processes have been devised, both the vapor phase and that the eilluent be convapor phase and liquid phase, for the isomerizadensed under conditions such that the amount of tion of normal parailins to the corresponding isohydrogen desired in the subsequent isomerization parains. Although the problem of inhibiting step be dissolved and that any excess hydrogen be cracking and degradation of the feed stocks and separated and recirculated. The hydrogenation the products of the reaction is less pronounced in and isomerization steps may be carried out at the the case of the isomerization of normal butane same pressure or the hydrogenation step may be to isobutane, when the higher homologues of norcarried out under a lower pressure than the mal butane are subjected to isomerization a isomerization in which case the ellluent from the real problem presents itself to limit and inhydrogenation is compressed to the pressure dehibit insofar as possible the cracking and degsired in the isomerization and any excess hydroradation of the reactants and the products gen separated and recycled. The solution of hyof the reaction. This necessarily is'a detriment to drogen' in the aromatic-free feed stock is then the commercial development of isomerization subjected to an isomerization treatment over an processes utilizing normal pentane, normal hexane 40 aluminum chloride catalyst in the presence'of a and the higher homologues as feed stocks to prohydrogen halide promoter and under liquid phase duce the corresponding branched chain isoparconditions and subsequently stripped of hydroailins. Generally less drastic reaction conditions, gen chloride and unused. hydrogen. The hydroamong which may be mentioned lower temperagen chloride-hydrogen mixture is recycled to the tures, are employed for the higher homologues of hydrogenation and/or isomerization reactors, or normal butane than are used when isomerizing desirably to the condenser where the eilluent from normal butane. Various expedients have been the hydrogenation is condensed. employed to increase catalyst life, such as pre- If desired the recycle streams may be subtreating the feed stocks to remove traces of water, jected tostripping, to treatment with caustic or oleflns, aromatic hydrocarbons and sulfur ancl 60 to any other method so as to remove the hydro- (Cl. m30-683.5)

sulfur compounds. Elemental or molecular hydrogen has been employed to minimize degradation of the catalyst and the removal of aromatic compounds by selective solvents such as liquid phase operation).

gen chloride before the stream enters the hydrogenation zone. Similarly the streams may lalso be treated to remove hydrogen sulde, for example by treatment with aluminum chloride.

The hydrogenation step may also be carried out in the liquid phase, preferably with multiple injection of hydrogen so as to dissolve the hydrogen as it is. consumed. In this embodiment the HCl-hydrogen mixture recycled from the isomerization zone is preferably introduced at one or more of the injection points.

The aluminum chloride catalyst used, in the isomerization step is preferably deposited on alumina which is desirably in a substantially completely dehydrated state, i. e. below 2% water. The alumina need not be pre-impregnated with aluminum chloride, although this is a desirable method of forming the catalyst mass. admixture of the alumina and aluminum chloride is sufficient. Suitable aluminas for use in conjunction with the present invention comprise alumina gel, activated alumina, Porocel, gibbsite,

bhmite and the like. In each case it is desirable 225 F., are employed for the isomerization, with contact times ranging between about ten minutes andabout f'lve hours, depending of course upon the specific temperature and other reaction conditions maintained. In pretreating the alumina carrier to partially remove the water contained therein, temperatures ranging between about 500 F. and about 1200 F. and times of contact of between about v30 minutes andV about l2 hours are usually suiicient to remove any water which might be given oi during the isomerization reaction. l

The aluminum chloride may be admixed with from 1 to 10 times its weight of the alumina carrier and heated to a temperature some 50 to 100 degrees in excess of the highest temperature to be employed in the isomerization reaction while passing therethrough a stream of inert gas such as nitrogen or carbon dioxide, or, if ldesired, vapors of normal butane or `otherlight hydrocarbon may be passed therethrough to purge loosely held and excess aluminum chloride from the pores of the alumina carrier. l A suitable catalyst for carrying out the isomerization process of the invention is prepared A simple propyl, butyl chlorides or bromides, may also be i employed. The amount of promoter present ranges usually between about 0.1 and about 10 weight per cent of the feed stock, and preferably between about 0.2 and about 2.0%. The present operation is carried out at temperatures between about 100 F. and about 300 F., preferably between about 150 F. and about 225 F.

'The conditions employed in the hydrogenaton step, as pointed out above, `are relatively mild. Suitable temperatures range from 200 to 400 F. and pressures from atmospheric to 50 atmospheres.

Referring now to Figure 1 a total naphtha cut from crude distillation is introduced into tower I and distilled to remove butane and lighter overhead through line 2. Pentane and heavier is taken from thev bottom of tower I through line 3 and introduced into a fractionation column l where a. cut is made at 200 F., materials boiling over 200 F. being removed through line 5 and used as feedstock for reforming or other processing. The light naphtha fraction boiling below 200 F. is removed overhead through line 6 and mixed with hydrogen introduced through line 1 in the ratio of 1500 cu. ft. of hydrogen per barrel of naphtha. The 'mixture of light naphtha and hydrogen is then introduced in the vapor phase into hydrogenaton zone 8 under the desired pressure for example, about 200 lbs. per sq. in. where it is contacted with a catalyst consisting of 2% palladium deposited on activated alumina at 400 F. The naphtha feed rate is 1.0 v./v./hr. (volumes naphtha per volume catalyst/hr.). zone 8 together with the unreacted hydrogen is withdrawn'through line 9, cooled in cooler II, and condensed in separator I2 where any undissolved hydrogen is removed through line I3 recompressed to 200 lbs. in compressor Ill and recycled to reactor 8. In this manner the products from the hydrogenaton unit are condensed under suflicient pressure so that all the hydrogen needed in the subsequent isomerization step is 'dissolved in the condensate. This condensate is passed through line I 4 to isomerization zone I5 where it contacts aluminum chloride adsorbed on alumina, at temperatures between 100 F. and 300 F.

Simultaneously with the introduction of the condensate into reactor I5, hydrogen chloride is introduced into the system through lines I6 and either branch lines I'I or I8. The hydrogen chloride is introduced at such a rate that a concentration of between 0.2% and 2.0% by weight based on the light naphtha charged to reactor I5 is at all times maintained in the catalyst mass. The reacted eilluent passes from reactor I5 through line I9 into stripping column 20 wherein by first heating Porocel to a temperature of about 1000 F. for 4 to 5 hours to drive off free and combined water to the extent that the nal catalyst carrier contains on the order of 1 to 3% of total water content. Aluminum .chloride in the amount of between 5 and 30 weight per cent of the carrier is then introduced into the catalyst mass under substantially operating conditions, by

hydrogen, hydrogen chloride and some hydrocarbon vapors are removed overhead through line 2| and may bel withdrawn from the system through line 22. Preferably, however, they are recycled to condenser-separator I2 by line 23. Alternatively they may be recycled in whole or in part through line 24 to hydrogenation reactor 8. Bottoms from stripper 20 are removed through line 25 and suitablyftreated to produce finished aviation or motor gasoline blending stocks. f s The 'following data illustrates the advantages yto be obtained by hydrogenating a normal hexane cut with ,2% palladium on activated alumina according to the teachings of this invention.

The eilluent from the hydrogenaton Run No 1 2 3 Hydrogenalion Conditions Catalyst v2% Pd on A110; 2%! ou 2- 3. Temperature, F 400 200 400 Pressure, lb./sq. n....... 50 atm. 50 Naphtha Feed Rate, v./v. 1. Hydrogen Feed Rate, CF/B l. 500 Length of Run, hours 6 6 4 Catalyst Age, hours 8 16 Product Inspections Feed Benzene Content, vol. percentbyU.V 6.0 l0.3 3.6 0.6 ASTM Clear Octane No..- 57. 4 48. l 57. 4 56. 8 Gravit API 73. 7 75.1 73.9 7i. 5 Napht a Distillatlon:

I. B. P., "F 153 153 153 151 154 154 158 208 99.0 0.6

1 Maximum value; may be high due to U. V. interference.

Run No 4 5 6 Feed Pretreatment Residual Benzene Content,

Vol. Per Cent. lsomerizatlon Results:

AST Clear Octane ber- Feed Product.

Increase.- Appearance oi Used Catalyst- Hydrogen-.nien

0.3 max 3. 6

60 13 3 Lt. Gray.

11i Lt. Gray.--. Green While the above process has been described in connection with the removal of aromatics from the feed to an isomerization-unlt, it may also be applied to the removal of any undesired unsaturated compound, for example, olens.

The nature and objects of the present invention having been thus described and illustrated, what is claimed as new and useful and is desired to be secured by Letters Patent is:

1. A process of isomerizing a light naphtha fraction containing oleiins and aromatics in the presence of aluminum chloride deposited on alumina and -a hydrogen halide promoter which comprises treating the light naphtha fraction in the vapor phase in a rst step with excess hydrogen under a pressure not more than 50 atmospheres, and a catalyst consisting of 2% palladium on alumina to saturate the olens and aromatics, condensing and cooling the hydrogenated light naphtha in the presence of the hydrogen and under the pressure to be used in a subsequent isomerzation step to substantially saturate the hydrogenated light naphtha with hydrogen at the pressure of the subsequent isomerizaton step, whereby a portion of the hydrogen dissolves therein, separating undissolved hydrogen and recycling it to the hydrogenation step, subjecting the light naphtha fraction in a second step in the presence of the dissolved hydrogen to the isomerizing action of the aluminum chloride and hydrogen halide, stripping hydrogen halide and hydrogen from the isomerized product and recycling the said hydrogen halide to the somerization step and recycling the said hydrogen to the hydrogenation step.

2. A process of isomerizing a light naphtha fraction containing olens and aromatics in the presence of aluminum chloride deposited on alumina and a hydrogen halide promoter which comprises treating the light naphtha fraction in the vapor phase at a pressure of 200 lbs. per sq. in. in `a rst step with excess hydrogen and a catalyst consisting of 2% palladium on alumina to saturate the oleflns and aromatics, condensing and cooling the hydrogenated light naphtha in the presence of the hydrogen Without releasing the pressure, whereby a portion of the hydrogen is dissolved in the condensate, separating undissolved hydrogen from the condensate, and recycling it to the hydrogenation step, subjecting the light naphtha fraction in a second step in the presence of the dissolved hydrogen to the isomerizing action of the aluminum chloride and hydrogen halide, stripping hydrogen halide and hydrogen from the isomerized product and recycling the said hydrogen halide to the isomerization step and the said hydrogen to the hydrogenation step.

STEPHEN F. PERRY;

REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS Number Name Date 1,965,956 Dunkel et al July 10, 1934 2,143,364 Taylor Jan. `10, 1939 2,181,640 Deanesly et al Nov. 28, 1939 2,299,716 Van Peski Oct. 20, 1942 2,327,593 De Simo et -al Aug. 24, 1943 2,390,883 Iverson Dec. 11, 1945 

1. A PROCESS OF ISOMERIZING A LIGHT NAPHTHA FRACTION CONTAINING OLEFINS AND AROMATICS IN THE PRESENCE OF ALUMINUM CHLORIDE DEPOSITED ON ALUMINA AND A HYDROGEN HALIDE PROMOTER WHICH COMPRISES TREATING THE LIGHT NAPHTHA FRACTION IN THE VAPOR PHASE IN A FIRST STEP WITH EXCESS HYDROGEN UNDER A PRESSURE NOT MORE THAN 50 ATMOSPHERES, AND A CATALYST CONSISTING OF 2% PALLADIUM ON ALUMINA TO SATURATE THE OLEFINS AND AROMATICS, CONDENSING AND COOLING THE HYDROGENATED LIGHT NAPHTHA IN THE PRESENCE OF THE HYDROGEN AND UNDER THE PRESSURE TO BE USED IN A SUBSEQUENT ISOMERIZATION STEP TO SUBSTANTIALLY SATURATE THE HYDROGENATED LIGHT NAPHTHA WITH HYDROGEN AT THE PRESSURE OF THE SUBSEQUENT ISOMERIZATION STEP, WHEREBY A PORTION OF THE HYDROGEN DISSOLVES THEREIN, SEPARATING UNDISSOLVED HYDROGEN AND RECYCLING IT TO THE HYDROGENATION STEP, SUBJECTING THE LIGHT NAPHTHA FRACTION IN A SECOND STEP IN THE PRESENCE OF THE DISSOLVED HYDROGEN TO THE ISOMERIZING ACTION OF THE ALUMINUM CHLORIDE AND HYDROGEN HALIDE, STRIPPING HYDROGEN HALIDE AND HYDROGEN FROM THE ISOMERIZED PRODUCT AND RECYCLING THE SAID HYDROGEN HALIDE TO THE ISOMERIZATION STEP AND RECYCLING THE SAID HYDROGEN TO THE HYDROGENATION STEP. 